Azo dye.



T 0 all whom it may concern:

UNITED' STATES PATENT OFFICE.

PAUL VOLKMANN, OF ELBERFELD, GERMANY, ASSIGNOR TO FARBENFABRIKEN VORM. FRIEDR. BAYER & 00., OF ELBERFELD, GERMANY, A CORPORATION OF GERMANY.

AZO DYE.

Specification of Letters iatent.

Patented Oct. 27, 1908.

Application filed June 1%, 1908. Serial No. 438,922.

Be it known that 1, PAUL VOLKMANN, doctor of philosophy, chemist, citizen of the German Empire, residing at Elberfeld, Germany;,Kingdom of Prussia, have invented new and usefulv Improvements in New Azo Dyes, of which the, following is a specification.

I have found that new and valuable az0-, dyestuffs dyeing the fiber from yellow to red to brown shades can be obtainedby combining diazocompounds with'sulfonic acids of 1-naphthyl3methyl-5-pyraZolones.

The new dyestufis are after being dried and pulverized in the shape of their sodium salts powders soluble in water'and soluble in concentrated sulfuric acid. They yield upon reduction with stannous chlorid and hydrochloric acid amins and sulfonic acids of 4- amino-1 naphthyl-3-methyL5-pyrazolones.

In carrying out my invention practically I give the following examples, the parts being by weight:

Example tized in the'usual manner by means of- 7 parts of sodium nitrite and thenecessary quantity of hydrochloric acid. The result 'ing diazo solution is then added to a solution which has to be well stirred of 38.2 parts of 1- beta naphthyl4.8disulfonic acid--3methly 5- pyrazolone in an excess of sodium carbonate. --After half an hour-the formation of the dyestuff is complete. The product of the reaction is heated to 70 C'. and the dyestuffis precipitated by the addition'of common salt, filtered off and dried. It dyes wool from acid baths invery level pure yellow shades fast to light.

Exam le 2.21.2 parts of toluidin are tetrazotize in the usualv manner by m'eans of and the necessary quantity of hydrochloric acid; the resulting 'tetrazo compound is then introduced into a well cooled solution of 76.4 arts'of 1-betanaphthlyl 4.8 disulfonic aci 3 methyl- 5 Y pyrazo one containing an excess of sodium :razotize compound is combined with a solution of I carbonate.

The dyestufi se arates during the reaction. It is filtered o anddried. It

dyes unmordanted cotton red shades of ex cellent fastness to acids;

vExample:? .18.4:p'arts of benzidin are tetin .the' us'u'al"way and ,the' tetrazotion of 38.2

1. 9.3 parts of anilin are diazo re see s eeev 13.8 parts of salicylic acid containing a slight excess of sodium carbonate. The formation of the intermediate compound is complete after24: hours. An alkaline soluarts of 1-betanaphthIyl4.8 disulfonic aci 3 methyl 5 yrazo one is added and the mixture is stirre for 12 hours. It is then heated, and thedyestufl is salted out, filtered off and dried. It dyes .unmordanted cotton very pure yellowish orange shades of good fastness to light.

In the following table the shades produced by some of the new dyestuffs are given:

Dyestufi: Dyes Wool:

ani1in+i-p-na hth l-i.s-disuiiomc acidyellow. 3-methyly5-p raz clone.

anilin+1-u.nap thyl-3.5.7-t ti 5 111 f o n l 0 yellow.

acid-3-methyl-S-pyrazolone.

para toluidin 1 p -naphthyl-6.8-disu.l-

ionic acid-3-methyl-5-pyrazolone. 2-.toluidin-5-sulfonic ac1d+1-Bnaphthyl- 4.8-disu1ionic acid-3-methyl-5-pyrazolone. meta-xylidin+ 1-;9-naphth l-6. 8-disu1fonic acid-3rmethyl-5-pyrazolone. 2.5 dichloroanilin+ 1 B -naplpthy1-6.8-disulfonic acid-3-methyl-5-pyrazolone. a-naphthylamin+ 1Bnaphthy14. 8-(11 sul-,

tonic acid-3-methyl-5-pyrazolone. 2-naphigiylamin-es-disultonic acid-l-l-flnaph hyl-4.8-disu1fonic acid-:i-methyl- .S-pyrazolone. 2-acetamino-4-toluidin+ 1-naphthol-4-su1- ionic acid (saponified)+1-B-naphthyliLS-disulfonic acid-3-metl1yl-5-pyrazoone. para-phenylenediamin-i-Z mol. l-fl-naphthy -4.8disulfonic acid-3-methyl-5-pyrazolone. 5-nitro-2-amino heuol or 5-nitro-4-chloro- 2-1iminopheno +1-B-naphtl1yl- 4.8-d1sulionic acicl-3-mcthyl-5-pyrazolone. para-aminoacetaniiid+ salicylic acid (acetyl group split ofi) +1-Bnaphthyl-4.& disulfonic acid-B-methyl-5-pyrazolone.

greeni sh-yellow.

yellow.

reddish-yellow.

greenish-yellow.

0 range.

reddish-yell ow.

red.

' red.

brown, chromed after dyeing: bluish-red. reddish o 1' a n g e, chromed at t e r dyeing: bluish red;

Dyes unmordanted cotton: reddish-yellow.

dehydrothiotoluidin sulfonic acid+ 1-3- naphthyl-4.8-disulionic acid-3-methylfi-pyraz clone.

salicylic acid. benzidin l-fi-naplithyl-is d. i 5 ul f o ni 0 orange.

benzidin acid-3-n1ethyl-5-pyrazol one.

= 2-amino-8-naphthol-6-sulfonic acid-azo-meta-phenylen ediamm.

black-brown. V

Having now described my invention and in what manner the same is to be performed, what I clalm is The herein-described newjazodyestufis, ob-

tainable by combining diazocompounds w th sulfonic acids of 1-naphthy1-3-methyl-5pyrazolones, which dyestuffs are after being dried and pulverized in the shape of theirso I In testimony whereof I have hereunto set dium salts powders soluble in Water and solumy hand in the presence of two subscribing 1Q ble in concentrated sulfuric acid; yielding witnesses.

upon reduction with 'stannous ch l0rid and V hydrochloric acid amins and sulfonic acids of PAUL VOLKLIANN s 4-amino-1na hth l=3-methyl-5-pyrazolones Witnesses:

and dyeing t e er from yellow to red to OTTO KijNIG,

Correction iWLGtiGIS Patent No. 902 ,186.

brown shades, substantially as described. WM; WASHINGTON BRUNSWICK.

It is hereby certified that in Letters Patent No. 992,186, granted October 2,7, 1908, upon the application of Paul Volkmann, of Elberfe1(i;'Germany, for an improvement in Azo' Dyes, an error appears in the printed specification requiring correction, as follows: In line 39, page l ithe word methly shouldreaii methyl; andthat the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oifice. I. v I I si ned and sealed this 17th day if November, A. 1).,- 1908; r i

SEAL 3 I I I I I o. o. BILL NGs;

' i Acting ommi mw ofPatentadried and pulverized in the shape of theirso I In testimony whereof I have hereunto set dium salts powders soluble in Water and solumy hand in the presence of two subscribing 1Q ble in concentrated sulfuric acid; yielding witnesses.

upon reduction with 'stannous ch l0rid and V hydrochloric acid amins and sulfonic acids of PAUL VOLKLIANN s 4-amino-1na hth l=3-methyl-5-pyrazolones Witnesses:

and dyeing t e er from yellow to red to OTTO KijNIG,

Correction iWLGtiGIS Patent No. 902 ,186.

brown shades, substantially as described. WM; WASHINGTON BRUNSWICK.

It is hereby certified that in Letters Patent No. 992,186, granted October 2,7, 1908, upon the application of Paul Volkmann, of Elberfe1(i;'Germany, for an improvement in Azo' Dyes, an error appears in the printed specification requiring correction, as follows: In line 39, page l ithe word methly shouldreaii methyl; andthat the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oifice. I. v I I si ned and sealed this 17th day if November, A. 1).,- 1908; r i

SEAL 3 I I I I I o. o. BILL NGs;

' i Acting ommi mw ofPatenta- Correction in Letters Patent No. 902,186.

It is hereby certified that in Letters Patent No. 902,186, granted October 27, 1908, upon the application of Paul Volkmann, of Elberfeld, Germany, for an improvement in the printed specification requiring correction, as follows: In line 30, page 1, the word methly should read methyl and that the said Letters Patent should be read with this correction therein that the same may conform i in Azo- Dyes, an error appears to the record of the case in the Patent Oflice.

Signed and sealed this 1m] day (31' November, A. 1)., 1903.

O. C. BILLINGS, Acting Commissioner of Patents.

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